Copolymers of ethylene/stilbene



United States Patent 015 3,338,877 Patented Aug. 29, 1967 ice 3,338,877COPOLYMERS F ETHYLENE/STILBENE William S. Anderson, Oakland, Calif.,assignor to Shell Oil Company, New York, N .Y., a corporation ofDelawhere x is an integer so that the total units making up of copolymerranges in molecular weight of from about 1000 to about 1,000,000,preferably between 2500 and 600,000 as determined by the lightscattering method and the inware 5 trinsic viscosity ranging from 0.15to 2, preferably be- No Drawing. Original application Dec. 9, 1963, Ser.No. tween and dL/gram- 329,295. Divided and this application Ma 31,1966, T new and novel copolymers of the p s Inven- Ser. No. 553,676 tionare prepared by copolymerizing stilbene and ethylene 6 Claims. (Cl.260-882) in the presence of a suitable solvent and an organo lithium 10catalyst at a temperature range from about 50 C. to 50 C. and at apressure between 5,000 p.s.i. and 100,000 ABSTRACT OF THE DISCLOSURE iCopolymers of ethylene and stilbene which are useful Y Suitable qSolvent mixtllres made reference to as lubricating oil additives areobtained by copolymeriza- In column (4) 13 mean? {nlxthre of from 10% totion thereof under high pressures in the presence of an 15 9 of Certamaxygen'contallllng COIHPPUIIdS Such as organo lithium catalyst and inthe presence of a solvent dhhethyl ether, dlethyl ether, dloxalletdlethyl ether of mixture consisting of an aromatic hydrocarbon and ad{ethylene glycol, hy f d1Ph e11y1eI1e 0X1de, 0r polar containingCompound; nitrogen compounds such as 'trlethylamlne ortrlethylenediamine or sulfur-containing compounds such as diethylsulfide, tetrahydrothiophene, etc., and from 90% to 10% This patentapplication is a division of patent applicaof an aromatic hydrocarbonSuch as banzene of toluene tion Ser. No. 329,295, filed Dec. 9, 1963,now Patent No. or the llke- 3 2 2 345 issued Nov. 1 19 The catalyst maybe an organo lithium such as an alkyl This invention relates to new andnovel copolymers of y lithium p h aa -a ethyl or normal or ethylene andstilbene and derivatives thereof for use as h h butyl, octyl hthlumPhehyl haphthyl multi-functional materials and in compositions ofmatter. mlxthres thereof- The h l may also be It is known thatindividually stilbene or ethylene can adflflhw compound Such a thehthlum adduct of be polymerized to form various products and articles ofdlphehyl ethylene or of h h h alpha'methyl manufacture. Polymers ofstilbene are rather low molecrehe hl lf also be an pha a dlllthlocompound such ular weight materials which are rather thermally unstableas lts'dlhthlo P lt6dlhthlo hexane and dil'ficult to work with. Also,its use as additives in when other. yp of lys s u h as the Fnedel-Craftslubricants, rubber, coating materials is limited because catalystZleglef type catalysts Or Other alkah metal of solubility andcompatibility with these materials and catalysis. o sodlum or mlxturqsthereof Wlth of whom? compositions. the presence of the above-mentionedsolvents and under It has now been discovered that an excellentoxidatively dlfiereht presslh'e h temphrathre chhdltiohs from that andthermally Stable high molecular polymer can be of the present inventlonresults 1n a dltferent end product tained by copolymerizing ethylene wih tilb under from the one made by the process of the present invention.particular controlled conditions. These conditions are: Particular a a fof the h f of the pmseht (1) reacting the two monomers in the mol ratioof 1:10 40 Vehtloh 15 then" T1g1d1tY and 111511 Impact Stffiflgth: Theto 10:1 preferably 2:1 to 5:1 of ethylene to stilbene, (2) followingexamples are illustrative of the present invenunder high pressure offrom 5,000 p.s.i. to 100,000 p.s.i., 3 at between 40 c. and 50 0.,preferably between Example I and 25 C', in 'f a p f 0f $01Vent n1 iX' Amixture of about 1 part of stilbene and 5 parts ethyltures of fiertalnoxygell'contalnlng 0f nltfPgen'contamlng one were introduced into apressure vessel containing Compounds and hydfocallbonsa and 111 thePresence about a -50 mixture of tetrahydrofuran and toluene. f an Organ)lithium Catalyst Such as a alkyl of my1 The entire mixture is reactedunder pressure of 11,800- llthium compound. The copolymers of thisinvention have 6 600 i d at a temperature of around 0 5 C a plurality ofhnlts represented y the formula: in the presence of 0.01 mole butyllithium catalyst for 50 1-24 hours, until the copolymer reactionindicated the f stilbene content to be essentially unchanged. Thestilbene MOHFCHZ CH CH- content of the copolymer was around 20-30% andthe molecular weight of the copolymer was between 10,000 and 100,000.

Following essentially the above procedure other cox polymers of thepresent invention were prepared as shown in Table I.

TABLE I Exarnple* stilbene, Ethylene, Reaction Reaction Reaction M01 wt.M01 M01 Temp, Pressure Time, Hr. (Ebul.) percent percent C.

II 35 Oto +5 11,s00-0,e00 10 5,000 III t. 25 10-15 13, 7009, 5 2,500 IV75 25 10-20 13, 500-0, 200 24 4,800 V 30 70 0-10 15, 000-1, 000 2410,000

V S0lvcnt=50l50 mixture of diethyl ether and toluene, Catalyst=litl1iumnaphthene Although the oil-solubility of these copolymers are marginal,their solubility and lubricating oil additive properties can be greatlyimproved by alkylation of the copolymer so as to introduce long alkylradicals having from 10 to over 30 carbon atoms. Alkylation of thecopolymer can be accomplished by reacting the copolymer in a suitablesolvent such as alkyl halides, e.g., ethyl chloride; nitroaromatics,e.g., nitrobenzene or carbon disulfide and the like, with long-chainolefins such as polyisobutylene, or C1040 alkyl halides or acetylhalides such as lauryl, oleyl, stearyl chlorides and the like. Thereaction can be carried out at from -50 C. to 20 C. and the reactiontime varies from 1 to 24 hours.

For example, the polymer of Example III was added to nitrobenzene,agitated and 20% of polyisobutylene (m.w. 1500) slowly added thereto andthe temperature maintained at -10 to -20 C. for about 5 hours. The endproduct (Ex. IIIA) contained units represented by the formulas:

wherein R is a polyisobutenyl radical.

Another way of increasing oil solubility is to hydrogenate the copolymerand this can be accomplished by dissolving the copolymer, e.g., Ex. I-Vin a hydrocarbon solvent such as cyclohexane and hyd'rogenating thecopolymer at 125200 C. and 500-1000 p.s.i. in the presence of a suitablecatalyst such as platinum.

For example, the copolymer of Ex. I was dissolved in cyclohexane andhydrogenated at 150-175 C., and 500800 p.s.i. pressure in the presenceof platinum catalyst for about 5-10 hours. About 60-75% of the aromaticunits in polymer were hydrogenated. The hydrogenated copolymer (Ex. IA)was soluble in mineral oil to -20 C. and lower whereas theunhydrogenated polymer was not soluble at these low temperatures. Thehydrogenated copolymer imparts pour point and viscosity index (VI)improving properties to mineral lubricating oil. Thus, a minerallubricating oil having a pour point of +20 and a VI of 50 was improvedby addition thereto to 5% of hydrogenated copolymer (Ex. IA) so that theoil composition has a pour point of 20 C. and a VI of 110.

When desired, additional improvements with respect to oxidationstability and scufling inhibition can be imparted to the oilcompositions containing the copolymers of this invention byincorporating small amounts (0.01 2%, preferably 0.1%-1%) of phenolicantioxidants such as alkylphenols, e.g., 2,6-ditertbutyl-4-methylphenolor p,p-methylene bisphenols such as 4,4-methylene bis(2,6- ditertbutylphenol) or arylamines such as phenylalphanaphthylamine, dialkyl sulfidesand mixtures thereof, e.g., dibenzyl disulfide, didodecyl sulfide.Anti-scufiing agents include organic phosphites, phosphates,phosphonates and their thio derivatives, such as alkyl phosphites, orphosphonates, e.g., diand tributyl, octyl, lauryl, stearyl, cyclohexyl,benzyl, cresyl, phenyl, phosphites or phosphates, as Well as their thioderivatives, P S -terpene reaction products, e.g., P S -pine oilreaction product and alkali metal salts thereof such as a potassium saltof a P S -terpene reaction product, phosphonates such as dibutylmethanephosphonate, dibutyl trichloromethanephosphonate, dibutylmonochloromethanephosphonate, di-butyl chlorobenzenephosphonate, and thelike. The full esters of pentavalent phosphorus acids such as triphenyl,tricresyl, trilauryl and tristearyl ortho-phosphates or potassium saltof P S -terpene reaction product are preferred.

The polymeric additives of this invention improve various mineral oilproducts by the incorporation of a minor amount (0.01% to 5%, preferably0.1% to 3% by weight) of the additive. Thus, they may be used to improvetransformer oils, turbine oils, hydraulic fluids, mineral lubricatingoils, industrial oils and the like. Suitably such lubricating oils rangefrom SAE 5W viscosity grade to SAE 140 grade and are derived fromparaffinic, naphthenic or asphaltic base crudes. Representative oils arerefined high viscosity index mineral oils having a viscosity at C. offrom 100 to 250 SUS.

Copolymers of the present invention possess excellent thermal stabilityproperties.

Copolymers of the present invention are compatible with waxes, rubber(natural and synthetic), moldable resins, ion exchange resins and can beused in radiation resistant oil, greases, plastics, dielectrics, opticalgoods, synthetic leather, drilling muds, lubricants and the like.

I claim as my invention:

1. A copolymer of ethylene and stilbene containing a plurality of unitsof the formula wherein R is a C to C alkyl radical, hydrogen, or apolyisobutenyl radical and having a molecular weight of from about 1000to about 1,000,000.

2. The copolymer of claim 1 wherein R is hydrogen.

3. The copolymer of claim 1 wherein one R in each of the plurality ofunits is a polyisobutenyl radical and the remaining R is apolyisobutenyl radical or hydrogen.

4. A process for preparing a copolymer of ethylene and stilbene having amolecular weight of from about 1000 to about 1,000,000 which comprisesreacting ethylene and stilbene in a mole ratio of from 1:10 to 10.1 at atempreature of from -40 C. to 50 C. and at a pressure of from 5,000 to100,000 p.s.i. in the presence of an organo lithium catalyst and asolvent mixture comprising an aromatic hydrocarbon and a compoundselected from the group consisting of dimethyl ether, diethyl ether,dioxane, diethyl ether of diethylene glycol, tetrahydrofuran,diphenylene oxide, triethylene amine, triethylenediamine, diethylsulfide and tetrahydrothiophene.

5. The process of claim 2 wherein the catalyst is butyl lithium and thesolvent mixture consists of equal amounts of tetrahydrofuran andtoluene.

6. The copolymer of claim 3 wherein both Rs are polyisobutenyl radicals.

No references cited.

J. L. SCHOFER, Primary Examiner. M. B. KURTZMAN, Assistant Examiner,

1. A COPOLYMER OF ETHYLENE AND STILBENE CONTAINING A PLURALITY OF UNITSOF THE FORMULA
 4. A PROCESS FOR PREPARING A COPOLYMER OF ETHYLENE ANDSTILBENE HAVING A MOLECULE WEIGHT OF FROM ABOUT 1000 TO ABOUT 1,000,000WHICH COMPRISES REACTING ETHYLENE AND STILBENE IN A MOLE RATION OF FROM1:10 TO 10.1 AT A TEMPERATURE OF FROM -40*C. TO 50*C. AND AT A PRESSUREOF FROM 5,000 TO 100,000 P.S.I. IN THE PRESENCE OF AN ORGANO LITHIUMCATALYST AND A SOLVENT MIXTURE COMPRISING AN AROMATIC HYDROCARBON AND ACOMPOUND SELECTED FROM THE GROUP CONSISTING OF DIMETHYL ETHER, DIETHYLETHER, DIOXANE, DIETHYL ETHER OF DIETHYLENE GLYCOL, TETRAHYDROFURAN,DIPHENYLENE OXIDE, TRIETHYLENE AMINE, THIETHYLENEDIAMINE, DIETHYLSULFIDE AND TETRAHYDROTHIOPHENE.